CN110376299A - The measuring method of diisopropyl naphthalene the amount of migration in silicone oil paper - Google Patents

The measuring method of diisopropyl naphthalene the amount of migration in silicone oil paper Download PDF

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Publication number
CN110376299A
CN110376299A CN201910548459.8A CN201910548459A CN110376299A CN 110376299 A CN110376299 A CN 110376299A CN 201910548459 A CN201910548459 A CN 201910548459A CN 110376299 A CN110376299 A CN 110376299A
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migration
solution
naphthalene
diisopropyl naphthalene
silicone oil
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Inventor
赵凯
褚晓敏
丁枫芸
洪苑
陈可君
马洁清
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HANGZHOU QUALITY TECHNOLOGY SUPERVISION INSPECTION INSTITUTE
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HANGZHOU QUALITY TECHNOLOGY SUPERVISION INSPECTION INSTITUTE
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Priority to CN201910548459.8A priority Critical patent/CN110376299A/en
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/04Preparation or injection of sample to be analysed
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/04Preparation or injection of sample to be analysed
    • G01N30/06Preparation
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/62Detectors specially adapted therefor
    • G01N30/72Mass spectrometers
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/86Signal analysis
    • G01N30/8624Detection of slopes or peaks; baseline correction
    • G01N30/8631Peaks
    • G01N30/8634Peak quality criteria
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/04Preparation or injection of sample to be analysed
    • G01N2030/042Standards
    • G01N2030/045Standards internal
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/04Preparation or injection of sample to be analysed
    • G01N30/06Preparation
    • G01N2030/062Preparation extracting sample from raw material

Abstract

The present invention relates to the measuring method of diisopropyl naphthalene the amount of migration in silicone oil paper, include the following steps: to configure diisopropyl naphthalene standard reserving solution, diethyl naphthalene internal standard stock solution, standards of alcohol working solution, oil base standard working solution;6dm2The silicone oil paper sample contact 1kg food simulants of area carry out migration test, and the simulated solution after pipetting migration is added sodium chloride and ethyl acetate, internal standard stock solution, ultrasonic extraction, supernatant liquid is taken to analyze for GC-MS in tool plug centrifuge tube;Ion detection is selected, inner mark method ration obtains the amount of migration of diisopropyl naphthalene.The present invention optimizes detection pre-treatment process, coded program, the selection of GC-MS chromatographic column and temperature program, substantially reduces the detection time of diisopropyl naphthalene the amount of migration, promotes working efficiency, while reducing detection limit.This method is simple and efficient, with excellent sensitivity and stability, meets analysis detection and accurate quantitative analysis to diisopropyl naphthalene the amount of migration in silicone oil paper.

Description

The measuring method of diisopropyl naphthalene the amount of migration in silicone oil paper
Technical field
The invention belongs to technical field of food safety detection, and in particular to diisopropyl naphthalene the amount of migration in a kind of silicone oil paper Measuring method.
Background technique
Silicone oil paper is a kind of wrapping paper, it is ubiquitous in life, has three-layer structure.First layer structure is base stock, Second layer structure is lamination, and third layer structure is silicone oil.Silicone oil paper has the characteristics that high temperature resistant, moisture-proof, grease proofing, therefore general more It is packed for food service industry.Silicone oil paper is tough, anti-extrusion, folding are rubbed, and can play the role of protecting commodity in packing article.? The silicone oil paper frequently encountered in daily life mainly has barbecue paper, roast duck wrapping paper and packaging bag of some food etc..
Diisopropyl naphthalene (DIPN) has outstanding advantages of colourless, tasteless, strong to dyestuff solvability, is widely used in paper Etc..Foreign study found that diisopropyl naphthalene is easy to cause to hurt to human body from moving in paper in dry food Evil.It is domestic at present less to diisopropyl naphthalene migration quantifier elimination report in silicone oil paper, have to the examination criteria of diisopropyl naphthalene Solvent extraction measures diisopropyl naphthalene (DIPN) content in EU criteria BS EN 14719:2005 paper pulp, paper and cardboard, The professional standard of China's entry and exit is using gas chromatography-mass spectrography (GC-MS) to food contact material paper and cardboard diisopropyl Naphthalene (DIPN) measurement.But it is relatively fewer for the measurement of the amount of migration.
Summary of the invention
The present invention overcomes deficiency in the prior art, it is to provide a kind of survey of diisopropyl naphthalene the amount of migration in silicone oil paper Determine method, this method is simple and efficient, with excellent sensitivity and stability.
The specific technical solution of the present invention is as follows:
The measuring method of diisopropyl naphthalene the amount of migration, includes the following steps: in silicone oil paper
Configure diisopropyl naphthalene standard reserving solution;
Configure diethyl naphthalene internal standard stock solution;
Configure standards of alcohol working solution;
Configure oil base standard working solution;
Sample pretreatment: area-method is used, 6dm is taken2The silicone oil paper sample of area, 6dm2The silicone oil paper sample of area contacts 1kg food simulants, 40-100 DEG C at a temperature of carry out the migration test of 2-5h, simulated solution after being migrated;
Simulated solution after pipetting migration is in tool plug centrifuge tube, addition sodium chloride and ethyl acetate into centrifuge tube, then plus Enter diethyl naphthalene internal standard stock solution, ultrasonic extraction takes supernatant liquid to analyze for GC-MS;
Ion detection is selected, inner mark method ration obtains the amount of migration of diisopropyl naphthalene in silicone oil paper sample.
Preferably, when supernatant is analyzed using GC-MS, chromatographic condition are as follows: chromatographic column (DB-5MS 30m × 0.25mm×0.25μm);Temperature program: 70 DEG C of holding 2min rise to 250 DEG C with 10 DEG C/min rate, keep 10min;Carrier gas: High-pure helium, purity >=99.999%;Input mode: Splitless injecting samples, 250 DEG C;Ionization mode: electronic and ionic source;Ionization Voltage: 70eV;Makings interface temperature: 300 DEG C.
Preferably, the food simulants are 50% ethyl alcohol, isooctane.
Preferably, it configures diisopropyl naphthalene standard reserving solution: weighing 30mg diisopropyl naphthalene standard items in 25ml volumetric flask In, scale is diluted to dehydrated alcohol.
Preferably, it configures diethyl naphthalene internal standard stock solution: weighing 50mg diethyl naphthalene standard items in 25ml volumetric flask, use Dehydrated alcohol is diluted to scale.
Preferably, it configures standards of alcohol working solution: measuring 0.1ml, 0.2ml, 0.5ml, 1.0ml, 2.0ml bis- respectively Dehydrated alcohol is added extremely in 5 25ml volumetric flasks in the diethyl naphthalene internal standard stock solution of isopropyl naphthalene standard reserving solution and 100ul Scale is spare.
Preferably, it configures oil base standard working solution: measuring 0.1ml, 0.2ml, 0.5ml, 1.0ml, 2.0ml bis- respectively Isooctane is added to quarter in 5 25ml volumetric flasks in the diethyl naphthalene internal standard stock solution of isopropyl naphthalene standard reserving solution and 100ul It spends spare.
Preferably, the simulated solution after pipetting 5.00mL migration has in plug centrifuge tube in 50mL, is separately added into centrifuge tube 0.5g sodium chloride and 5mL ethyl acetate, add 20uL diethyl naphthalene internal standard stock solution, and ultrasonic extraction 15min takes supernatant Liquid is analyzed for GC-MS.
Detection pre-treatment process and coded program is optimized in the present invention, the selection and liter by GC-MS chromatographic column The optimization of warm program substantially reduces the detection time of diisopropyl naphthalene the amount of migration, promotes working efficiency, while reducing detection Limit.This method is simple and efficient, with excellent sensitivity and stability, meets and migrates to diisopropyl naphthalene in silicone oil paper (DIPN) The analysis detection and accurate quantitative analysis of amount.
Detailed description of the invention
Fig. 1 is diisopropyl naphthalene the amount of migration (μ g/L) and migrates the relationship (isooctane) of temperature.
Specific embodiment
Further illustrate that the present invention, the present invention do not refer to that part is the prior art with reference to embodiments.
Instrument and equipment
Agilent 7890A gas chromatograph: Agilent company, the U.S..
Agilent 5975C gas chromatograph-mass spectrometer: Agilent company, the U.S..
Milli-Q ultrapure water instrument: Millipore company, the U.S..
N-EVP-12 nitrogen concentrating instrument: the U.S..
KQ300DB ultrasonic cleaner: Kunshan Ultrasonic Instruments Co., Ltd..
RE-5299 type Rotary Evaporators: Shanghai Yarong Biochemical Instrument Plant.
Reagent
Ethyl acetate: HPLC grades, Sigma Co., USA.
Dehydrated alcohol: HPLC grades, German Merck company.
Isooctane: HPLC grades, German Merck company.
Diisopropyl naphthalene (DIPN) standard items: purity >=97.0% (mass fraction), Town in Shanghai compose company.
Diethyl naphthalene standard items: internal standard compound, purity >=97.0% (mass fraction), Town in Shanghai compose company.
Sample pretreatment of the present invention is referring to " GB 31604.1-2015 national food safety standard food contacts material Material and product migration test general rule ".
Migrate influence of the temperature to object the amount of migration
According to the difference of silicone oil paper packaged food type, selects isooctane to carry out migration experiment as food simulants, move It moves experimental temperature and selects 0-100 DEG C, transit time is 2h.By taking DIPN in sample as an example, temperature is migrated to object the amount of migration Influence it is as shown in Figure 1.The result shows that effect is best under 40-100 DEG C of transition condition and is not much different by DIPN, it is preferred that move Moving temperature is 40 DEG C.
Effect of extracting of the different simulated solutions to different substrates
When choosing n-hexane, methylene chloride, acetonitrile, 50% ethyl alcohol and isooctane as analogies respectively, to the extraction of DIPN Take capability result as shown in table 1, the results showed that, DIPN can migrate two different matrix in 5 kinds of simulated solutions, wherein 50% ethyl alcohol and isooctane migration effect in corresponding matrix are best, and the migration effect of methylene chloride, acetonitrile, ethyl acetate Generally, therefore the present invention chooses 50% ethyl alcohol and isooctane and carries out as simulated solution.
Effect of extracting of the different simulated solutions of table 1 to different substrates
The influence of transit time
Reference sample pre-treatment step, using the rate of recovery as index, respectively investigate extraction time 40min, 80min, The influence (being shown in Table 2) of 120min, 160min and 300min to migration effect, the results showed that, transit time 40min, the rate of recovery exists 53.5%-66.8%;Transit time 80min, the rate of recovery is in 79.86%-82.77%;Transit time 120min, recycling Rate is in 93.69%-95.88%, and transit time is more than 120min, and the rate of recovery is not significantly increased, therefore transit time selects 120-300min, preferred transit time are 120min (2h).
Influence of 2 transit time of table to the DIPN rate of recovery
Linear relationship and precision
Diisopropyl naphthalene standard reserving solution is taken, a certain amount of internal standard solution is added, dilutes step by step respectively, draws standard curve, is made Linear regression analysis (referring to conventional method in the art).DIPN 0.1-100 mg/kg sample introduction concentration range in two kinds of matrix Interior corresponding peak area is in a linear relationship, and related coefficient is all larger than 0.995, obtains the range of linearity of each substance, regression equation, The RSD of peak area when related coefficient and 2 kinds of target substance concentrations are 10 μ g/L is shown in Table 3.
3 DIPN of table in two kinds of matrix the range of linearity, regression equation, related coefficient (r) and peak area RSD
The rate of recovery, detection limit and quantitative limit
Detection limit (LOD) and quantitative limit (LOQ) are determined respectively according to 3 times and 10 times of signal-to-noise ratio (S/N), in negative sample base 0.5,5.0,50.0,200.0mg/L 4 horizontal mixed standard solutions are added in matter, are located in advance by sample pretreatment step Reason, each horizontal replication 6 times obtain the average recovery of standard addition of DIPN, detection limit and quantitative limit (being shown in Table 4).Detection limit For 0.5mg/kg, it is quantitatively limited to 1.0mg/kg;And the average recovery of standard addition of DIPN is in the case where 4 various concentration mark-ons are horizontal 82.0%-95.34% can satisfy the detection demand of diisopropyl naphthalene in silicone oil paper (DIPN).
Average recovery of standard addition, RSD, detection limit and the quantitative limit of different substrates DIPN in 4 silicone oil paper of table
Embodiment
The measuring method of diisopropyl naphthalene the amount of migration, includes the following steps: in silicone oil paper
Configuration diisopropyl naphthalene standard reserving solution: 30mg diisopropyl naphthalene standard items are weighed in 25ml volumetric flask, with nothing Water-ethanol is diluted to scale.
Configuration diethyl naphthalene internal standard stock solution: 50mg diethyl naphthalene standard items are weighed in 25ml volumetric flask, with anhydrous second Alcohol is diluted to scale.
It configures standards of alcohol working solution: measuring 0.1ml, 0.2ml, 0.5ml, 1.0ml, 2.0ml diisopropyl naphthalene respectively It is standby to scale that dehydrated alcohol is added in 5 25ml volumetric flasks in the diethyl naphthalene internal standard stock solution of standard reserving solution and 100ul With.
It configures oil base standard working solution: measuring 0.1ml, 0.2ml, 0.5ml, 1.0ml, 2.0ml diisopropyl naphthalene respectively It is spare to scale that isooctane is added in 5 25ml volumetric flasks in the diethyl naphthalene internal standard stock solution of standard reserving solution and 100ul.
Sample pretreatment: area-method is used, 6dm is taken2The silicone oil paper sample of area, select 50% ethyl alcohol, isooctane as Food simulants, 6dm2The silicone oil paper sample of area contacts 1kg food simulants, 40 DEG C at a temperature of carry out the migration examination of 2h It tests, the simulated solution after being migrated;
Simulated solution after pipetting 5.00mL migration has in plug centrifuge tube in 50mL, and 0.5g chlorine is separately added into centrifuge tube Change sodium and 5mL ethyl acetate, adds 20uL diethyl naphthalene internal standard stock solution, ultrasonic extraction 15min takes supernatant liquid to be used for GC-MS analysis.
Chromatographic condition are as follows: chromatographic column (30m × 0.25mm × 0.25 μm DB-5MS);Temperature program: 70 DEG C of holding 2min, 250 DEG C are risen to 10 DEG C/min rate, keeps 10min;Carrier gas: high-pure helium, purity >=99.999%;Input mode: it does not shunt Sample introduction, 250 DEG C;Ionization mode: electronic and ionic source;Ionizing voltage: 70eV;Makings interface temperature: 300 DEG C.Each compound Mass spectrum acquisition parameter is shown in Table 5.
Each compound mass spectrometry parameters condition of table 5
Ion detection is selected, inner mark method ration obtains the amount of migration of diisopropyl naphthalene in silicone oil paper sample.
The present invention establishes gas chromatography-mass spectrography (GC-MS) measurement of diisopropyl naphthalene in silicone oil paper (DIPN).Two The range of linearity of isopropyl naphthalene (DIPN) the amount of migration is 0.1-100mg/kg;Detection is limited to 0.5mg/kg;Quantitative limit is (with signal-to-noise ratio >=10 meters) it is 1.0mg/kg;In the case where 3 mark-ons are horizontal, average recovery of standard addition is 82.0%-95.34%, relative standard deviation For 2.08%-3.95% (n=6).This method is simple and efficient, with excellent sensitivity and stability, meets in silicone oil paper The analysis detection and accurate quantitative analysis of diisopropyl naphthalene (DIPN) the amount of migration.

Claims (8)

1. the measuring method of diisopropyl naphthalene the amount of migration in silicone oil paper, it is characterised in that include the following steps:
Configure diisopropyl naphthalene standard reserving solution;
Configure diethyl naphthalene internal standard stock solution;
Configure standards of alcohol working solution;
Configure oil base standard working solution;
Sample pretreatment: area-method is used, 6dm is taken2The silicone oil paper sample of area, 6dm2The silicone oil paper sample contact 1kg food of area Product analogies, 40-100 DEG C at a temperature of carry out the migration test of 2-5h, simulated solution after being migrated;
Sodium chloride and ethyl acetate are added into centrifuge tube, adds two in tool plug centrifuge tube for simulated solution after pipetting migration Ethylnaphthalene internal standard stock solution, ultrasonic extraction take supernatant liquid to analyze for GC-MS;
Ion detection is selected, inner mark method ration obtains the amount of migration of diisopropyl naphthalene in silicone oil paper sample.
2. measuring method according to claim 1, which is characterized in that when supernatant is analyzed using GC-MS, chromatostrip Part are as follows: chromatographic column (DB-5MS30m × 0.25mm × 0.25 μm);Temperature program: 70 DEG C of holding 2min, with 10 DEG C/min rate liter To 250 DEG C, 10min is kept;Carrier gas: high-pure helium, purity >=99.999%;Input mode: Splitless injecting samples, 250 DEG C;Ionization Mode: electronic and ionic source;Ionizing voltage: 70eV;Makings interface temperature: 300 DEG C.
3. measuring method according to claim 2, which is characterized in that the food simulants are 50% ethyl alcohol, isooctane.
4. measuring method according to claim 1 or 2 or 3, which is characterized in that configuration diisopropyl naphthalene standard reserving solution: 30mg diisopropyl naphthalene standard items are weighed in 25ml volumetric flask, are diluted to scale with dehydrated alcohol.
5. measuring method according to claim 4, which is characterized in that configuration diethyl naphthalene internal standard stock solution: weigh 50mg Diethyl naphthalene standard items are diluted to scale in 25ml volumetric flask, with dehydrated alcohol.
6. measuring method according to claim 5, which is characterized in that configuration standards of alcohol working solution: measure respectively The diethyl naphthalene internal standard stock solution of 0.1ml, 0.2ml, 0.5ml, 1.0ml, 2.0ml diisopropyl naphthalene standard reserving solution and 100ul In 5 25ml volumetric flasks, it is spare to scale that dehydrated alcohol is added.
7. measuring method according to claim 6, which is characterized in that configuration oil base standard working solution: measure respectively The diethyl naphthalene internal standard stock solution of 0.1ml, 0.2ml, 0.5ml, 1.0ml, 2.0ml diisopropyl naphthalene standard reserving solution and 100ul In 5 25ml volumetric flasks, it is spare to scale that isooctane is added.
8. measuring method according to claim 7, which is characterized in that the simulated solution after pipetting 5.00mL migration has in 50mL It fills in centrifuge tube, 0.5g sodium chloride and 5mL ethyl acetate is separately added into centrifuge tube, add the storage of 20uL diethyl naphthalene internal standard Standby liquid, ultrasonic extraction 15min take supernatant liquid to analyze for GC-MS.
CN201910548459.8A 2019-06-24 2019-06-24 The measuring method of diisopropyl naphthalene the amount of migration in silicone oil paper Pending CN110376299A (en)

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Application publication date: 20191025